Tungsten carbide / bismuth tungstate photoelectrocatalytic material prepared by spin-coating method and preparation method of tungsten carbide / bismuth tungstate photoelectrocatalytic material

Abstract

The invention discloses a tungsten carbide / bismuth tungstate photoelectric catalytic material prepared by a spin-coating method and a preparation method thereof. The preparation method comprises the following steps: preparing bismuth tungstate powder; preparing WxC powder; respectively dissolving bismuth tungstate powder and WxC powder in the membrane solution; a liquid dropping system of a spin coater is started, the WxC solution and the BWO solution prepared in the fifth step are sequentially dropped to the center position of a cleaned ITO substrate, and the WxC solution and the BWO solution are naturally air-dried in air to obtain the tungsten carbide / bismuth tungstate photoelectrocatalysis material on the surface of the conductive ITO; the material obviously improves the sunlight utilization rate; good photoelectrocatalysis performance is shown in an alkaline electrolyte; according to the BWO / WxC composite material disclosed by the invention, a Bi2O3 framework derived from bismuth nitrate can prevent WxC from being oxidized, so that the composite catalyst shows good stability.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of functional materials, and relates to a photoelectrocatalytic material, in particular to a tungsten carbide / bismuth tungstate photoelectrocatalytic material prepared by a spin coating method and a preparation method thereof. BACKGROUND

[0002] The photoelectrocatalytic water splitting reaction is composed of two half reactions, namely, water oxidation reaction occurring at the photoanode and water reduction reaction occurring at the cathode, that is, under illumination, an external voltage is used to force the photo-generated electrons to move to the opposite electrode, thereby spatially separating the photo-generated holes and electrons, prolonging the lifetime of the photo-generated carriers, generating oxygen at the photoanode, and generating hydrogen at the cathode. Bismuth tungstate (Bi2WO6) is often used as a preferred photoelectrocatalytic water splitting catalyst material due to its unique structural properties, mainly because it is composed of (Bi2O2) 2+ oxide layers and WO6 octahedral sheets alternately form a layered crystal structure, which is more conducive to the transfer of electrons and holes in different directions and limits the recombination of electrons and holes to a certain extent; and the narrow band gap of Bi2WO6 is located at about 2.7eV, thereby exhibiting excellent photocatalytic activity under certain conditions. However, its practical application still faces some key challenges, such as high carrier recombination rate and slow surface reaction kinetics, resulting in low PEC (photoelectrochemical) water oxidation efficiency.

[0003] Tungsten carbide (WC) has similar d-band electron density states and surface electronic properties as platinum (Pt), which enables it to exhibit activity comparable to noble metals in catalytic reactions, thereby providing a good catalytic basis for water splitting reactions. Tungsten carbide is limited by the preparation process, and the product has a disordered morphology, irregular particle size, uneven dispersion, and is prone to incomplete reaction and agglomeration, which greatly affects its performance as a water splitting catalyst. SUMMARY

[0004] In view of the deficiencies of the prior art, the purpose of the present application is to provide a tungsten carbide / bismuth tungstate photoelectrocatalytic material prepared by a spin coating method and a preparation method thereof. The photoelectrocatalytic material exhibits high photoelectrocatalytic performance in an alkaline electrolyte, and the preparation method is simple and controllable.

[0005] To achieve the above purpose, the technical scheme adopted by the present application is as follows:

[0006] A preparation method of a tungsten carbide / bismuth tungstate photoelectrocatalytic material prepared by a spin coating method, comprising the following steps:

[0007] Step one, bismuth nitrate pentahydrate and sodium tungstate are added to deionized water respectively, and stirred until dissolved to obtain solution A and solution B with a concentration of 0.1-1mol / L;

[0008] Step two, take the solution A and solution B mixed in equal volume ratio after loading into polytetrafluoroethylene lining high pressure reactor, the sealed reactor into homogeneous hydrothermal reaction instrument, set temperature parameters for 160-200℃, reaction time is 10-20h, after the reaction is cooled to room temperature, the final reaction product filter washing, drying after grinding to get BWO powder;

[0009] Step three, according to the molar ratio of 1:1:2 to take the zinc nitrate, 2-methyl imidazole and sodium tungstate is dissolved in methanol solution, loading into polytetrafluoroethylene lining high pressure reactor, the sealed reactor into homogeneous hydrothermal reaction instrument, set temperature parameters for 120-200℃, reaction time is 4-8h, after the reaction is cooled to room temperature, the final reaction product filter washing, drying after grinding to get precursor WO4 - -ZIF-8 powder;

[0010] Step four, the precursor WO4 - -ZIF-8 powder prepared in step three is put into the porcelain boat, placed in the furnace in the argon hydrogen mixed atmosphere with 5-10℃ / min rate to 700-1000℃, then the furnace is cooled to room temperature, get WxC powder;

[0011] Step five, respectively take 50mg of bismuth tungstate powder prepared in step two and WxC powder prepared in step four is dissolved in 500 microliter membrane solution respectively to get WxC solution and BWO solution;

[0012] Step six, open the spin coater drop system, WxC solution and BWO solution prepared in step five are dropped in the center position of the cleaned ITO substrate in turn, air dry to obtain tungsten carbide / bismuth tungstate photoelectric catalytic material on the conductive ITO surface.

[0013] Preferably, the stirring in step one is magnetic stirring for 10-24h.

[0014] Preferably, the volume filling ratio of the high pressure reactor lining in step two is 40%-60%.

[0015] Preferably, the filter washing in step two and step three is deionized water filter washing 3-5 times.

[0016] Preferably, the drying in step two and step three is put into 40-70℃ vacuum oven or freeze drying box for 12-24h.

[0017] Preferably, the grinding in step two and step three is grinding in the mortar for 15-30min.

[0018] Preferably, the volume ratio of hydrogen in the argon-hydrogen mixed gas in step four is 10%.

[0019] Preferably, the cleaning method of the ITO substrate in step six is to sequentially use acetone and ethanol to ultrasonically clean the ITO substrate, then rinse it with deionized water, and finally dry it with nitrogen.

[0020] The application also protects a tungsten carbide / bismuth tungstate photoelectric catalytic material prepared by the spin coating method.

[0021] Compared with the prior art, the application has the following technical effects:

[0022] The application first prepares bismuth tungstate (BWO) and tungsten carbide (WxC) materials with good crystallinity, and then prepares a BWO / WxC composite material by a spin coating method; the narrow band gap (~2.8eV) of the bismuth tungstate (BWO) and the metallic conductivity of the tungsten carbide (WxC) synergistically act, a Schottky junction is constructed through a BWO / WxC interface, the separation efficiency of photo-generated electron-hole pairs is improved by 3-5 times, the visible light absorption range can be widened to 600nm, and the solar light utilization rate is significantly improved; the Fermi level of the tungsten carbide is close to the hydrogen evolution potential (HER), and can be used as an electron trap to inhibit the recombination of photo-generated carriers; under the action of centrifugal force during the spin coating, the BWO and WxC particles or molecules in the solution can quickly spread on the ITO surface to form a thin film with uniform thickness and no obvious agglomeration, so that the nano-particle loading of the tungsten carbide can expose more W-C bond unsaturated sites, the surface active sites are enhanced, the surface acidic sites (Lewis acid) promote the dissociation and adsorption of water molecules, the adsorption free energy of the hydrogen intermediate (H*) tends to 0 (ΔG H* ≈0), the overpotential of the HER is reduced, and the prepared BWO / WxC photoelectric catalyst exhibits good photoelectric catalytic performance in an alkaline electrolyte;

[0023] The BWO / WxC composite material of the application can prevent the oxidation of WxC through the Bi2O3 framework derived from bismuth nitrate, so that the composite catalyst exhibits good stability. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The XRD pattern of the BWO prepared in Example 1 is shown in the figure;

[0025] Figure 2 The XRD pattern of the WxC prepared in Example 1 is shown in the figure;

[0026] Figure 3 The SEM photo of the BWO prepared in Example 1 is shown in the figure;

[0027] Figure 4 The SEM photo of the WxC prepared in Example 1 is shown in the figure;

[0028] Figure 5 is a BWO / WxC prepared in Example 1, and the photoelectrocatalytic performance under the condition of pH = 9.5 is shown in the figure. DETAILED DESCRIPTION

[0029] The specific content of the present application is further explained in detail in the following examples.

[0030] In the following examples, the film solution used is Komo D520, 5% (mass percentage concentration), and the manufacturer is Shanghai Hesen Electric Co., Ltd.

[0031] The ITO conductive glass sheet used has a thickness of 1.1 mm and a size of 20 mm*10 mm. The ITO conductive glass is processed and made by using a magnetron sputtering method to coat a layer of indium tin oxide (commonly known as ITO) film on the basis of a sodium-calcium substrate or a silicon-boron substrate glass.

[0032] The volume ratio of hydrogen in the argon-hydrogen mixed gas used is 10%.

[0033] Example 1

[0034] The present embodiment gives a preparation method of a tungsten carbide / bismuth tungstate photoelectrocatalytic material prepared by spin coating, comprising the following steps:

[0035] Step one, take 5 mol of bismuth nitrate pentahydrate and 5 mol of sodium tungstate and add them to 100 mL of deionized water respectively, stir for 12 h using a magnetic stirrer until dissolved, to obtain solution A and solution B with a concentration of 0.5 mol / L;

[0036] Step two, mix solution A and solution B in equal volume ratio, then load into a polytetrafluoroethylene-lined high-pressure reaction kettle, the volume filling ratio of the high-pressure reaction kettle lining is 50%, put the sealed reaction kettle into a homogeneous hydrothermal reaction instrument, set the temperature parameter to 1800℃, the reaction time is 12 h, after the reaction is completed, cool to room temperature, use deionized water to filter and wash the final reaction product 5 times, put it into a 70℃ vacuum oven to dry for 24 h, then grind in a mortar for 15 min to obtain BWO powder;

[0037] Step three, take 5 mol of zinc nitrate, 5 mol of 2-methylimidazole and 10 mol of sodium tungstate and dissolve them in 50 mL of methanol solution in equal molar ratio, load into a polytetrafluoroethylene-lined high-pressure reaction kettle, put the sealed reaction kettle into a homogeneous hydrothermal reaction instrument, set the temperature parameter to 160℃, the reaction time is 6 h, after the reaction is completed, cool to room temperature, use deionized water to filter and wash the final reaction product 3 times, put it into a 40℃ vacuum oven to dry for 24 h, then grind in a mortar for 15 min to obtain WO4--ZIF-8 precursor powder;

[0038] Step 4: Place the precursor WO4--ZIF-8 powder prepared in Step 3 into a ceramic boat, place it in a muffle furnace, and heat it to 900°C at a rate of 5°C / min under an argon-hydrogen mixed atmosphere. Then, allow it to cool naturally to room temperature with the furnace to obtain WxC powder.

[0039] Step 5: Dissolve 50 mg of bismuth tungstate powder prepared in Step 2 and WxC powder prepared in Step 4 in 500 μL of membrane solution to obtain WxC solution and BWO solution, respectively.

[0040] Step 6: Turn on the drop system of the spin coater and drop the WxC solution and BWO solution prepared in step 5 onto the center of the cleaned ITO substrate in sequence. Allow it to air dry naturally to obtain the tungsten carbide / bismuth tungstate photocatalytic material on the conductive ITO surface. The ITO substrate is cleaned by ultrasonic cleaning with acetone and ethanol in sequence, then rinsed with deionized water, and finally dried with nitrogen.

[0041] Figure 1 The XRD pattern of the BWO prepared in Example 1; as shown Figure 1 As shown, the XRD pattern corresponds to the standard diffraction data of BiWO in PDF#39-0256 and BiO3 in PDF#76-2478, indicating that bismuth tungstate (BWO) was successfully prepared.

[0042] Figure 2 The XRD pattern of WxC prepared in Example 1 is shown; Figure 2 As shown, W x C exhibits multiple diffraction peaks; comparison reveals that W... x Some diffraction peaks of C overlap or are close to the standard peaks of W2C, W, and WC, indicating that W2C and WC phases and elemental W coexist in the sample.

[0043] Figure 3 These are SEM images of the BWO prepared in Example 1; as shown Figure 3 As shown, BWO exhibits a distinct flower-like structure, which is composed of numerous stacked thin sheets with gaps between them. These gaps can affect the mass transfer and diffusion properties of the material. The overall size of the flower-like structure is slightly less than 3 μm, and its surface is rough with many fine bumps and textures, which increases the specific surface area of ​​the material, which is beneficial to improving the catalytic performance of the material.

[0044] Figure 4 These are SEM images of WxC prepared in Example 1; as shown Figure 4 As shown, W x Material C exhibits a bulk structure and a rough surface, which gives it a large specific surface area, facilitating the transport of active substances in photoelectrocatalysis.

[0045] Figure 5 is a plot of the photoelectrocatalytic performance of the BWO / WxC prepared in Example 1 under the condition of pH = 9.5. In a conventional three-electrode system (BWO / WxC / ITO electrode as the working electrode, mercury / mercury oxide electrode as the reference electrode, and platinum electrode as the counter electrode), the electrolyte is a buffer solution (pH = 9.5) prepared using sodium tetraborate pharmaceuticals, and the resulting photocurrent density-voltage (J-V) curve is tested using a photoelectrochemical test system (PEC 2000, Pelli). As shown in FIG. 1, the photocurrent density of Example 1 reaches 0.24 mA cm-2at an overpotential of 1.23 V. Figure 5 -2 The photoelectrocatalytic performance is optimal, and the photo-generated electrons and holes are rapidly and effectively separated under light conditions.

[0046] Example 2:

[0047] This embodiment gives a preparation method of a tungsten carbide / bismuth tungstate photoelectrocatalytic material prepared by a spin coating method, comprising the following steps:

[0048] Step one, 1 mol of bismuth nitrate pentahydrate and 1 mol of sodium tungstate are respectively added to 100 mL of deionized water, stirred for 10 h using a magnetic stirrer until dissolved, to obtain solution A and solution B, both with a concentration of 0.1 mol / L;

[0049] Step two, solutions A and B are mixed in equal volume ratio and then loaded into a polytetrafluoroethylene-lined high-pressure reaction kettle, the volume filling ratio of the lining of the high-pressure reaction kettle is 60%, the sealed reaction kettle is placed in a homogeneous hydrothermal reaction instrument, the temperature parameter is set to 200°C, and the reaction time is 10 h, after the reaction is completed, it is cooled to room temperature, the final reaction product is washed with deionized water for 3 times, dried in a 40°C vacuum oven for 24 h, and then ground in a mortar for 30 min to obtain bismuth tungstate powder;

[0050] Step three, 1 mol of zinc nitrate, 1 mol of 2-methylimidazole, and 2 mol of sodium tungstate are dissolved in 50 mL of methanol solution in equal molar ratio, and loaded into a polytetrafluoroethylene-lined high-pressure reaction kettle, the sealed reaction kettle is placed in a homogeneous hydrothermal reaction instrument, the temperature parameter is set to 120°C, and the reaction time is 8 h, after the reaction is completed, it is cooled to room temperature, the final reaction product is washed with deionized water for 5 times, dried in a 70°C vacuum oven for 12 h, and then ground in a mortar for 30 min to obtain precursor WO4--ZIF-8 powder;

[0051] Step four, the precursor WO4--ZIF-8 powder prepared in step three is placed in a porcelain boat and placed in a muffle furnace, heated to 1000°C at a rate of 10°C / min under an argon-hydrogen mixed gas atmosphere, and then naturally cooled to room temperature with the furnace to obtain WxC powder;

[0052] ​Step five, 50 mg of the bismuth tungstate powder prepared in step two and the WxC powder prepared in step four were dissolved in 500 microliters of the film solution respectively to obtain WxC solution and BWO solution;

[0053] Step six, the drop system of the spin coater was opened, and the WxC and BWO solutions prepared in step five were dropped in the center of the cleaned ITO substrate in sequence, and then naturally air dried to obtain the tungsten carbide / bismuth tungstate photoelectrocatalytic material on the conductive ITO surface; the cleaning method of the ITO substrate was to sequentially use acetone and ethanol to ultrasonically clean the ITO substrate, then rinse with deionized water, and finally dry with nitrogen.

[0054] Example 3:

[0055] The present embodiment gives a preparation method of a tungsten carbide / bismuth tungstate photoelectrocatalytic material prepared by a spin coating method, comprising the following steps:

[0056] Step one, 10 mol of bismuth nitrate pentahydrate and 10 mol of sodium tungstate were respectively added into 100 mL of deionized water, and stirred by a magnetic stirrer for 20 h until dissolved to obtain solution A and solution B with a concentration of 1 mol / L;

[0057] Step two, the solution A and the solution B were mixed in equal volume ratio, and then loaded into a polytetrafluoroethylene-lined high-pressure reaction kettle, the volume filling ratio of the lining of the high-pressure reaction kettle was 40%, the sealed reaction kettle was put into a homogeneous hydrothermal reaction instrument, the temperature parameter was set to 160℃, and the reaction time was 20 h, after the reaction was completed, the final reaction was cooled to room temperature, and then filtered and washed with deionized water for 4 times, dried in a 60℃ vacuum oven for 12 h, and then ground in a mortar for 20 min to obtain bismuth tungstate powder;

[0058] Step three, 2 mol of zinc nitrate, 2 mol of 2-methylimidazole and 4 mol of sodium tungstate were dissolved in 50 mL of methanol solution in equal molar ratio, and loaded into a polytetrafluoroethylene-lined high-pressure reaction kettle, the sealed reaction kettle was put into a homogeneous hydrothermal reaction instrument, the temperature parameter was set to 200℃, and the reaction time was 4 h, after the reaction was completed, the final reaction was cooled to room temperature, and then filtered and washed with deionized water for 4 times, dried in a 60℃ vacuum oven for 18 h, and then ground in a mortar for 20 min to obtain a precursor WO4--ZIF-8 powder;

[0059] Step four, the precursor WO4--ZIF-8 powder prepared in step three was placed in a porcelain boat and placed in a muffle furnace, heated to 800℃ at a rate of 8℃ / min under argon-hydrogen mixed gas atmosphere, and then naturally cooled to room temperature with the furnace to obtain a WxC powder;

[0060] Step five, 50 mg of bismuth tungstate powder prepared in step two and WxC powder prepared in step four are respectively dissolved in 500 microliters of film solution to obtain WxC solution and BWO solution;

[0061] Step six, the drop system of the spin coater is turned on, and the solutions of WxC and BWO prepared in step five are sequentially dropped at the center position of the cleaned ITO substrate, and then naturally air-dried to obtain a tungsten carbide / bismuth tungstate photoelectrocatalytic material on the conductive ITO surface; the cleaning method of the ITO substrate is to sequentially use acetone and ethanol to ultrasonically clean the ITO substrate, then rinse with deionized water, and finally dry with nitrogen.

[0062] Example 4:

[0063] The present embodiment provides a preparation method of a tungsten carbide / bismuth tungstate photoelectrocatalytic material prepared by a spin coating method, comprising the following steps:

[0064] Step one, 2 mol of bismuth nitrate pentahydrate and 2 mol of sodium tungstate are respectively added into 100 mL of deionized water, and stirred for 24 h by a magnetic stirrer until dissolved to obtain solution A and solution B with a concentration of 0.2 mol / L;

[0065] Step two, solutions A and B are mixed in equal volume ratio and then loaded into a polytetrafluoroethylene-lined high-pressure reaction kettle, the volume filling ratio of the lining of the high-pressure reaction kettle is 50%, the sealed reaction kettle is placed into a homogeneous hydrothermal reaction instrument, the temperature parameter is set to 170°C, and the reaction time is 16 h, after the reaction is completed, the final reaction product is cooled to room temperature, filtered and washed with deionized water for 5 times, placed into a 70°C freeze-drying oven for drying for 18 h, and then ground in a mortar for 30 min to obtain bismuth tungstate powder;

[0066] Step three, 4 mol of zinc nitrate, 4 mol of 2-methylimidazole and 8 mol of sodium tungstate are dissolved in 50 mL of methanol solution in equal molar ratio, and then loaded into a polytetrafluoroethylene-lined high-pressure reaction kettle, the sealed reaction kettle is placed into a homogeneous hydrothermal reaction instrument, the temperature parameter is set to 140°C, and the reaction time is 7 h, after the reaction is completed, the final reaction product is cooled to room temperature, filtered and washed with deionized water for 5 times, placed into a 40°C freeze-drying oven for drying for 24 h, and then ground in a mortar for 30 min to obtain a precursor WO4--ZIF-8 powder;

[0067] Step four, the precursor WO4--ZIF-8 powder prepared in step three is placed into a porcelain boat and placed in a muffle furnace, heated to 700°C at a rate of 10°C / min under an argon-hydrogen mixed atmosphere, and then naturally cooled to room temperature with the furnace to obtain a WxC powder;

[0068] Step five, 50 mg of the bismuth tungstate powder prepared in step two and the WxC powder prepared in step four were dissolved in 500 microliters of the film solution respectively to obtain a WxC solution and a BWO solution;

[0069] Step six, the drop system of the spin coater was opened, and the WxC and BWO solutions prepared in step five were dropped in sequence at the center position of the cleaned ITO substrate, and the tungsten carbide / bismuth tungstate photoelectrocatalytic material on the conductive ITO surface was obtained by natural air drying in the air. The cleaning method of the ITO substrate was to sequentially use acetone and ethanol to ultrasonically clean the ITO substrate, then rinse it with deionized water, and finally dry it with nitrogen.

Claims

1. A method for preparing tungsten carbide / bismuth tungstate photocatalytic materials by spin coating, characterized in that, Includes the following steps: Step 1: Add bismuth nitrate pentahydrate and sodium tungstate to deionized water and stir until dissolved to obtain solution A and solution B, each with a concentration of 0.1-1 mol / L. Step 2: Mix solutions A and B in equal volume ratio and place them into a polytetrafluoroethylene-lined high-pressure reactor. Place the sealed reactor into a homogeneous hydrothermal reactor and set the temperature parameters to 160-200℃ and the reaction time to 10-20h. After the reaction is completed, cool to room temperature, filter, wash, dry and grind the final reactant to obtain BWO powder. Step 3: Dissolve zinc nitrate, 2-methylimidazole and sodium tungstate in methanol solution according to a molar ratio of 1:1:2, and put the solution into a polytetrafluoroethylene-lined high-pressure reactor. Place the sealed reactor into a homogeneous hydrothermal reactor, set the temperature parameters to 120-200℃, and the reaction time to 4-8h. After the reaction is completed, cool to room temperature, filter, wash, dry and grind the final reactant to obtain the precursor WO4--ZIF-8 powder. Step 4: Place the precursor WO4--ZIF-8 powder prepared in Step 3 into a ceramic boat, place it in a muffle furnace, and heat it to 700-1000℃ at a rate of 5-10℃ / min under an argon-hydrogen mixed atmosphere. Hold it at this temperature for 2 hours, and then let it cool naturally to room temperature with the furnace to obtain WxC powder. Step 5: Take 50 mg of the bismuth tungstate powder prepared in Step 2 and the WxC powder prepared in Step 4, respectively, and dissolve them in 500 μL of membrane solution to obtain WxC solution and BWO solution. Step 6: Turn on the drop system of the spin coater and drop the WxC solution and BWO solution prepared in step 5 onto the center of the cleaned ITO substrate in sequence. Allow it to air dry naturally to obtain tungsten carbide / bismuth tungstate photoelectrocatalytic material on the conductive ITO surface.

2. The preparation method of the tungsten carbide / bismuth tungstate photocatalytic material prepared by spin coating as described in claim 1, characterized in that, The stirring described in step one involves stirring with a magnetic stirrer for 10–24 hours.

3. The preparation method of the tungsten carbide / bismuth tungstate photocatalytic material prepared by spin coating as described in claim 1, characterized in that, The volumetric filling ratio of the high-pressure reactor liner described in step two is 40% to 60%.

4. The preparation method of the tungsten carbide / bismuth tungstate photocatalytic material prepared by spin coating as described in claim 1, characterized in that, The filtration and washing described in steps two and three involves using deionized water for filtration and washing 3 to 5 times.

5. The preparation method of the tungsten carbide / bismuth tungstate photocatalytic material prepared by spin coating as described in claim 1, characterized in that, The drying process described in steps two and three involves placing the item in a vacuum oven or freeze dryer at 40–70°C for 12–24 hours.

6. The method for preparing tungsten carbide / bismuth tungstate photocatalytic material by spin coating as described in claim 1, characterized in that, The grinding described in steps two and three involves grinding in a mortar for 15 to 30 minutes.

7. The preparation method of the tungsten carbide / bismuth tungstate photocatalytic material prepared by spin coating as described in claim 1, characterized in that, In step four, the volume percentage of hydrogen in the argon-hydrogen mixture is 10%.

8. The method for preparing tungsten carbide / bismuth tungstate photocatalytic material by spin coating as described in claim 1, characterized in that, The cleaning method for the ITO substrate described in step six is ​​to use acetone and ethanol to ultrasonically clean the ITO substrate in sequence, then rinse it with deionized water, and finally dry it with nitrogen gas.

9. A tungsten carbide / bismuth tungstate photoelectrocatalytic material prepared by spin coating as described in any one of claims 1 to 8.

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